JP2003147085A - Compatibilizing agent, radical-copolymerizable unsaturated resin composition, molding material and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compatibilizing agent capable of improving a compatibility of more various radical-copolymerizable unsaturated resins with an addition polymerization-based polymer (a thermoplastic resin), and enabling the maintenance of a highly stable dispersed state for a long period. SOLUTION: This compatibilizing agent is to make the radical- copolymerizable unsaturated resins compatible with the addition polymerization- based polymers, and consists of (A) a graft copolymer obtained by bonding (A2) a silicon-based polymer chain containing a polyorganosiloxane as an indispensable component and (A3) a polymer chain consisting mainly of a polyoxyalkylene ether, polyester and/or polycarbonate with (A1) a chain consisting of a styrene-based monomer as a main component and obtained by a polymerization reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel compatibilizing agent capable of compatibilizing a radical copolymerizable unsaturated resin and an addition polymerization type polymer added mainly for the purpose of reducing shrinkage, improving physical properties, and the like. The present invention relates to a radical copolymerizable unsaturated resin composition, a molding material and a molded article. More specifically, unsaturated polyester resin, vinyl ester resin, radical copolymerizable unsaturated resin such as vinyl urethane resin, polystyrene,
The compatibility of the two components with addition polymerization polymers such as polymethylmethacrylate, styrene-butadiene rubber, polyvinylacetate, acrylic rubber, etc. is significantly improved, and problems in storage and molding due to poor compatibility are solved. The present invention relates to an extremely effective compatibilizer. Furthermore, by preventing the separation of the resin mixture containing the radical copolymerizable unsaturated resin and the addition-polymerization polymer, and allowing a stable dispersion state, that is, one liquefaction, a high added value of the product can be obtained. The present invention relates to a compatibilizer, a radical-copolymerizable unsaturated resin composition, a molding material and a molded article that can be achieved.

[0002]

2. Description of the Related Art Radical copolymerizable unsaturated resins are preferably used as raw materials for molding materials. However, a molding material using a radical copolymerizable unsaturated resin has a big problem that the volume shrinkage that occurs during curing causes a warp or crack of the molded product. For the purpose of improving this problem, various thermoplastic resins, for example, a shrinkage reducing agent such as polystyrene and styrene-butadiene rubber have been added to the molding material. However, these shrinkage reducing agents have low compatibility with the radical copolymerizable unsaturated resin, and segregation over time after mixing is unavoidable. Therefore, the dispersion stability in the molding material is poor, and the one-liquefying molding material is used. Making it difficult. Therefore, in a molded article obtained from such a molding material, various molding appearance defects such as scumming and color unevenness due to separation of the low-contracting agent are likely to occur.

Therefore, the present inventors have proposed a compatibilizer containing a copolymer having a specific structure in order to solve such a problem. That is, JP 2001-19
In 2456, a method of using as a compatibilizing agent containing a polystyrene block copolymer obtained by a condensation reaction method, and in JP 2001-213967 A, a polystyrene graft copolymer obtained by addition polymerization is contained. The method used as a compatibilizer is proposed. However, these compatibilizers, when added to a general radical copolymerizable unsaturated resin, show a high compatibilizing effect and can maintain a stable dispersed state for a long period of time. It was found that depending on the type, there are cases in which a sufficient effect cannot be expressed. Recently, there has been a demand from the market for a compatibilizer capable of exhibiting highly stable dispersion even when added to a larger amount of radically copolymerizable unsaturated resin.

[0004]

The object of the present invention is to provide a wide variety of radically copolymerizable unsaturated resins such as low polar unsaturated polyesters modified with hydrogenated bisphenol A, dicyclopentadiene, etc. The compatibility with the addition polymerization type polymer (thermoplastic resin) which is added mainly for the purpose of shrinking is further improved, and the molding defects due to the separation of the two components generated during storage and during the curing process are reduced. Another object of the present invention is to provide a compatibilizing agent capable of maintaining a highly stable dispersed state for a long period of time in a mixed liquid of more kinds of resins. That is, it is difficult to achieve in the prior art, to provide a compatibilizer that prevents the separation of a wider variety of radical copolymerizable unsaturated resins and addition polymerization type polymers, and enables the liquefaction of the resin mixture. It is in. Furthermore, a practical compatibilizer capable of eliminating defects (scumming, uniform colorability, smoothness, gloss) due to separation, a radical copolymerizable unsaturated resin composition containing the same, and a molding material. And to provide molded products.

[0005]

As a result of intensive studies on these problems, the present inventors have found that a graft copolymer having a specific structure is extremely useful as the above-mentioned compatibilizer, and the present invention Arrived

That is, the present invention is a compatibilizing agent for making a radical copolymerizable unsaturated resin and an addition polymerization type polymer more compatible with each other, and is obtained by a polymerization reaction using a styrene monomer as a main component. Graft in which a chain (A1) is bonded with a silicon-based polymer chain (A2) containing a polyorganosiloxane as an essential component and a polymer chain (A3) containing a polyoxyalkylene ether, polyester and / or polycarbonate as a main component. The present invention relates to a compatibilizer containing a copolymer (A), a radical copolymerizable unsaturated resin composition containing the compatibilizer, a molding material and a molded article.

Further, the present invention is a graft obtained by linking a polymer chain (A2) and a polymer chain (A3) to a chain (A1) via a (meth) acryloyl group or a styryl group bonded to each polymer chain. The copolymer (A), preferably the above graft copolymer (A) in which the number average molecular weight of the polymer chains (A2) and (A3) is 1,000 to 20,000, and preferably the chain (A1) and the polymer chain (A).
The weight ratio (A1 / A2 / A3) of 2) and (A3) is 90.
/0.1/9.9 to 20/20/60 of the above graft copolymer (A), more preferably an unsaturated monomer containing a styrene-based monomer forming a chain (A1) as a main component, A compatibilizer containing the above graft copolymer (A) obtained by addition-copolymerizing a macromonomer having a (meth) acryloyl group or a styryl group at one end of the polymer chains (A2) and (A3) , A useful radical copolymerizable unsaturated resin composition containing the same, a radical copolymerizable unsaturated resin, a polymerizable unsaturated monomer and / or an addition polymerization type polymer, and this radical copolymerizable unsaturated resin composition. The present invention relates to a molding material containing the same and a molded product thereof. The present invention will be described in detail below.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compatibilizing agent of the present invention comprises a polymer chain (A2) containing a polyorganosiloxane as an essential component in a chain (A1) obtained by addition polymerization of a styrene-based monomer as a main component, and a polyoxysilane. A graft copolymer (A) containing an alkylene ether chain, a polyester and / or a polycarbonate as a main component, and preferably a polymer chain (A3) having an oxyethylene-unit (unit) as a main constituent is bonded. It is a thing. In the graft copolymer (A), the polymer chain (A
2) and (A3) are preferably bonded to the chain (A1) via a (meth) acryloyl group or a styryl group (vinylbenzyl group) bonded to one end of (A2) and (A3).

The chain (A1) constituting the graft copolymer (A) is a polymer chain containing a styrene-based monomer as a main component, and the polymer chain (A2) and the polymer chain (A
3) is bound. The chain (A1) also incorporates an ethylenically unsaturated group derived from the polymer chain (A2) and the polymer chain (A3) when the polymer chain (A3) is bonded. The number average molecular weight of the chain (A1) is not particularly limited as long as the object of the present invention is achieved, but preferably 2000 to 80,000,
More preferably, it is 5000-30000.

As the monomer component that can be used to form the chain (A1), a styrene-based monomer alone or a styrene-based monomer as a main component and a (meth) acrylic acid-based monomer or the like as another component are used in combination. It is a mixture. As typical examples of such styrene-based monomers, styrene, vinyltoluene (methylstyrene), p-methylstyrene, t-butylstyrene,
Chlorostyrene, vinylbenzyl alkyl ether, vinylbenzyl alcohol, vinylbenzylamine, p-
Vinylphenol etc. are mentioned. When the styrene-based monomer is the main component of the chain (A1), when it is mixed with the radical copolymerizable unsaturated resin, the compatibility and stability are excellent and desirable.

Further, as typical examples of the (meth) acrylic acid type monomer which can be used in combination, known (meth) acrylic acid,
(Meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyethyl, (meth) acrylic acid hydroxypropyl, (meth) acrylic acid hydroxybutyl, (meth) acrylic acid glycidyl, (meth) acrylic acid glyceryl carbonate, methacrylic acid Isocyanate ethyl and (meth) acrylic acid ester can be used. To give only representative examples of (meth) acrylic acid alkyl esters, methyl (ethyl) (meth) acrylate, propyl, butyl, cyclohexyl, t-butylcyclohexyl, benzyl, phenyl, isobornyl, dicyclopentanyl, Examples thereof include ester compounds such as stearyl, behenyl, and trifluoroethyl.

Further, unsaturated carboxylic acid compounds such as fumaric acid and itaconic acid, (meth) acrylic acid ester monomers having functional groups such as hydroxyl groups and glycidyl ether groups, N
Maleimide monomers such as phenylmaleimide, acrylamide monomers such as acrylamide, vinyl carboxylic acid ester monomers such as vinyl benzoate, fumaric acid diester monomers, itaconic acid mono- and diester monomers. A monomer and a vinyl ether-based monomer such as cyclohexyl vinyl ether can also be used in combination. These can be appropriately selected and used as needed.

The content of the styrenic monomer as the main component in the chain (A1) is not particularly limited, but usually the styrenic monomer is 50% by weight or more, preferably 7%.
It is 0 to 99% by weight. Usually, the chain (A1) is composed of 70 to 99.9% by weight of a styrenic monomer and 0.1 to 30% by weight of another unsaturated monomer including a (meth) acrylic acid ester. The constituent components of the chain (A1) can be appropriately changed depending on the synthesis method and the required performance.

The polymer chain (A2) has a structure having a silicon-based polymer chain containing polyorganosiloxane as a main component and having a site capable of binding to the chain (A1) at one end of the polymer chain. Specifically, the polymer chain (A2) is composed of a portion other than the ethylenically unsaturated group incorporated in the chain (A1), that is, a silicon-based polymer chain containing polyorganosiloxane and a bonding site linked to the end thereof. Is a part excluding the ethylenically unsaturated group. More specifically, for example, all the moieties except the ethylenically unsaturated group of the (meth) acryloyl group linked to the polymer chain end containing polyorganosiloxane and all the moieties except the ethylenically polymerizable group of the styryl group are It is a polymer chain (A2). Polymer chain (A2)
Preferably has a number average molecular weight of 1,000 to 20,000,
More preferably, it is 1000 to 10,000.

The structure of the polymer chain (A2) is not particularly limited and may be a linear structure or a branched structure. The polymer chain may contain a polyether segment or a polyester segment in addition to the polyorganosiloxane segment, and they are appropriately selected and used so that the desired performance is exhibited. The content of the polyorganosiloxane in the polymer chain (A2) (excluding the bonding portion with the chain (A1)) is preferably 50% by weight or more, more preferably 80 to 98% by weight. The polyorganosiloxane component functions to control the solubility of the graft copolymer (A) itself in the resin mixture and stabilize the compatibilizing effect, and also contributes to the reduction of the interfacial energy. It is thought that it is doing.

The polymer chain (A3) is mainly composed of at least one selected from polyoxyalkylene ether, polyester and polycarbonate, and has a structure having a site capable of binding to the chain (A1) at one end of the polymer chain. It is a thing. Specifically, the polymer chain (A3) is a portion other than the ethylenically unsaturated group incorporated in the chain (A1), that is, a portion composed of a polymer chain and a binding site linked to the end thereof, and is an ethylenically unsaturated group. It consists of the part excluding the group. More specifically, all the moieties except the ethylenically unsaturated group of the (meth) acryloyl group linked to the polymer chain end and all the moieties except the ethylenically polymerizable group of the styryl group are polymer chains (A3). Is. The number average molecular weight of the polymer chain (A3) is preferably 1000 to 2
0000, more preferably 3000 to 10000. The synthesizing method, structure, etc. are not particularly limited.

The polymer chain (A3) preferably contains polyoxyalkylene ether as a main component. As a component that can be used to form the polyoxyalkylene ether, a ring-opening polymerizable monomer can be used, preferably ethylene oxide as a main component, ethylene oxide alone or another alkylene oxide copolymerizable with ethylene oxide. Or other ring compound capable of ring-opening copolymerization. Examples of other alkylene oxides include propylene oxide, butylene oxide, cyclohexene oxide, tetrahydrofuran, styrene oxide and the like. In particular, polyoxyalkylene ether having an oxyethylene unit as a main component is preferable.

In addition, as other cyclic compounds which can be ring-opening copolymerized with the above-mentioned ethylene oxide, acid anhydride compounds such as succinic anhydride and phthalic anhydride can be mentioned. Further, examples of the cyclic ester compound include caprolactone, valerolactone and the like. Further, cyclic carbonate compounds such as ethylene carbonate, propylene carbonate, trimethylene carbonate and the like can also be mentioned.
Other than the cyclic compound, carbon dioxide that can be copolymerized with alkylene oxide can also be used.

Regarding the polymer chain (A3) containing ethylene oxide as a main component and a polyoxyalkylene ether as a main component obtained by copolymerizing another cyclic compound,
It is not particularly limited as long as it exhibits compatibility with the radical copolymerizable unsaturated resin, and a random copolymer or block copolymer of polyethylene oxide and another cyclic compound may be used. Further, the polymer chain (A3) may be extended by using an ethylene oxide-based polyether polyol compound or glycol compound having a molecular weight of less than 1000 and a dicarboxylic acid compound, a diisocyanate compound, a carbonic acid ester compound, a diglycidyl ether compound or the like. Good. The polymer chain (A3) may be linear or branched, but is preferably linear due to the synthetic method.

Oxyethylene-in the polymer chain (A3)
The content of the unit (excluding the portion bonded to the chain (A1)) is preferably 20 to 100% by weight, particularly preferably 60 to 100% by weight. The remaining components are preferably non-oxyethylene polyoxyalkylene ethers, polyesters and / or polycarbonates. This is because the main component, oxyethylene chain, is closely coordinated with the radical copolymerizable unsaturated resin by intermolecular force, acts as an anchor component, and becomes an extremely important component in stable dispersion. Of course, the components other than the oxyethylene chain are designed, selected, and used so as to enhance the desired compatibilizing effect or impart an effect other than compatibilizing.

The number average molecular weight of the polyoxyalkylene ether of the polymer chain (A3) is preferably in the range of 1,000 to 20,000. Within this range, the performance as a compatibilizer is high and the synthesis is easy. Particularly preferably, the number average molecular weight is 3,000 to 8,000.

The polyester is a saturated and / or unsaturated polyester obtained from α, β-unsaturated dicarboxylic acid or saturated dicarboxylic acid and polyhydric alcohol, or polycaprolactone obtained by ring-opening polymerization of caprolactone or the like. . Examples of the polycarbonate include a polycarbonate obtained by reacting a polyhydric alcohol with a carbonic acid ester compound such as dimethyl carbonate, a polycarbonate obtained by ring-opening polymerization of a cyclic carbonic acid ester compound such as trimethylene carbonate, and the like. These may be used alone or in combination of two or more.

Examples of the α, β-unsaturated dicarboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, and dimethyl esters thereof. These α, β-unsaturated dicarboxylic acids may be used alone or in combination of two or more. Examples of the saturated dicarboxylic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid,
Examples thereof include het acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid and succinic anhydride. These saturated dicarboxylic acids may be used alone or in combination of two or more.

On the other hand, as the polyhydric alcohol, for example,
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2methyl-1,3 propanediol, 1,6
-Hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-
Pentanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, tricyclodecane dimethanol, alkylene oxide adduct of hydrogenated bisphenol A, diol such as glycols such as alkylene oxide adduct of bisphenol A, trimethylol Examples include triols such as propane and tetraols such as pentaerythritol. These polyhydric alcohols may be used alone or in combination of two or more.

The method for producing the compatibilizing agent containing the graft copolymer (A) in the present invention is not particularly limited, but for example, 1) only the chain (A1) is previously synthesized and separately prepared. A method in which the synthesized polymer chains (A2) and (A3) are combined by a polymer reaction to obtain the desired (A), 2)
The unsaturated monomer constituting (A1) and the polymer chain (A
There is a method of obtaining the target (A) by addition-copolymerizing 2) and (A3) with a macromonomer having a structure in which a polymerizable functional group capable of copolymerization is previously introduced at one end. A preferred method for producing the compatibilizing agent of the present invention is the synthesis method 2) in which a macromonomer that can easily obtain a homogeneous polymer is used.

As the macromonomer which can be preferably used for producing the compatibilizing agent of the present invention, the above-mentioned polyorganosiloquinsan chain (A2) and polyoxyalkylene ether, polyester and / or polycarbonate chain (A
3) having a polymerizable functional group at one end, and the polymerizable functional group can be copolymerized with the unsaturated monomer constituting the chain (A1). The functional group is preferably an ethylenically unsaturated group. Specifically, a (meth) acryloyl group and a styryl group are preferable from the viewpoint of polymerizability,
Other examples include vinyl group, propenyl group, allyl group, vinyl ether group and allyl ether group. A compound having these functional groups chemically bound to only one end of the polymer chain (A2) and A3) is
This is a typical example of macromonomer that can be used in the present invention.

Specifically, as the polyorganosiloxane-based macromonomer, mono (meth) acrylic acid ester of polydimethylsiloxane, monovinylbenzyl ether of polydimethylsiloxane, mono (meth) polydimethylsiloxane-polyethylene oxide block polymer is used. Acrylic acid esters and the like can be mentioned, and a compound in which a hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate and a polydimethylsiloxane having a hydroxyl group terminal are bonded with a diisocyanate compound such as isophorone diisocyanate can also be used.

As the polyether macromer, mono (meth) acrylic acid ester of polyethylene oxide, monovinyl benzyl ether of polyethylene oxide,
Monovinyl ether of polyethylene oxide, monoallyl ether of polyethylene oxide, monotonic acid ester of polyethylene oxide, equimolar reaction product of isocyanatoethyl methacrylate and polyethylene oxide, and hydroxyl group-containing unsaturated monoester such as hydroxyethyl (meth) acrylate. A compound in which a monomer and polyethylene oxide are bound by a diisocyanate compound such as isophorone diisocyanate can also be used. In addition, examples of the polyester macromer include mono (meth) acrylic acid ester of polycaprolactone, and examples of the polycarbonate macromonomer include mono (meth) acrylic acid ester of polytrimethylene carbonate. As a result, the detailed chemical structure of the entire macromonomer is not limited as long as the graft copolymer (A) that functions as the compatibilizer for the purpose of the present invention is obtained.

In the graft copolymer (A) which is the main component of the compatibilizing agent of the present invention, the polymer chains (A2) and (A
The chemical structure of the free terminal of 3) and the structure of the other terminal group other than the terminal having the polymerizable functional group of the macromonomer described above are not particularly limited. The end derived from the conditions for chain synthesis may be left as it is, or the end may be chemically converted to another structure. The terminal functional group is preferably a hydroxyl group, an alkoxy ether group, an alkoxy ester group, or an alkyl group. In particular, in the polymer chain (A3), when the molecular weight of the bonding portion with the chain (A1) significantly increases, the content of oxyethylene-units (units) in the polymer chain (A3) decreases,
The compatibilizing effect may become unstable. Therefore, in terms of the number of carbon atoms, a polymer chain (A3) having a structure of the binding part of 20 or less and 500 or less in molecular weight is preferable.

Chains (A in the graft copolymer (A)
1), the weight% ratio (A1 / A2 / A3) of the polymer chain (A2) and the polymer chain (A3) is preferably 90/0.
1 / 9.9 to 20/20/60, more preferably 80
/ 1/19 to 40/10/50. In particular, since the compatibilizing effect changes dramatically depending on the content of the polymer chain (A2), it is necessary to perform sufficient optimization by combining the radical copolymerizable unsaturated resin and the addition polymerization type polymer.

The number average molecular weight of the graft copolymer (A) is not particularly limited, but is preferably 2000-1.
It is desirable that it is 00000, more preferably 8000 to 50,000. Within this molecular weight range, the effect as a compatibilizer will be higher.

The number average molecular weight in the present invention refers to a value obtained by measuring with a polystyrene standard by gel permeation chromatography (GPC).

The synthesis reaction of the graft copolymer (A) of the compatibilizing agent of the present invention may be carried out in a solvent or may not be carried out, but usually from the viewpoint of workability, it is carried out in the solvent. Done. As the solvent, any solvent may be used as long as it can dissolve the compatibilizing agent and does not hinder the synthesis of the graft copolymer. After the reaction, the copolymer (A) may be isolated from the solvent as a solid component or may be a solution of the reaction solvent. In particular, if there is no problem in using it as a compatibilizer, it is preferable to use it as a solution. Further, for the purpose of lowering the solution viscosity and improving convenience, it is possible to dilute or redissolve with an unsaturated monomer such as styrene or an organic solvent other than the reaction solvent. For example, the compatibilizer composition containing the graft copolymer (A) and the reaction solvent is used.

The polymerization initiator at the time of synthesizing the graft copolymer (A) is not particularly limited, but generally, a radical polymerization type initiator, for example, an organic peroxide such as benzoyl peroxide or AIBN ( Azo compounds such as azobisisobutyronitrile) can be used. If the desired polymer is obtained, an anion or cation polymerization initiator other than the radical polymerization system can be used.

The compatibilizing agent of the present invention is blended with a radical copolymerizable unsaturated resin and an addition polymerization type polymer (thermoplastic resin) added as a low-contracting agent or a physical property-improving agent. The solubility can be improved. The addition amount of the compatibilizing agent is not particularly limited as long as it improves the compatibility between the radical copolymerizable unsaturated resin and the addition polymerization type polymer, but the addition amount of the radical copolymerization unsaturated resin and the addition polymerization type polymer is not limited. 10 in total
It is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 3 parts by weight, based on 0 parts by weight. With such an amount, the compatibilizing effect is higher, and the physical properties of the cured product are preferable.

The radical copolymerizable unsaturated resin composition in the present invention is, for example, a radical copolymerizable unsaturated resin such as unsaturated polyester, vinyl ester resin, vinyl urethane resin, or acrylic resin, addition polymerization type resin. It is composed of a polymer and a polymerizable unsaturated monomer.

The composition of the unsaturated polyester that can be used in the present invention is not particularly limited, and α, β-unsaturated dicarboxylic acid or α, β-unsaturated dicarboxylic acid optionally containing a saturated dicarboxylic acid is used. It is obtained from polyhydric alcohol. As the α, β-unsaturated dicarboxylic acid and the saturated dicarboxylic acid, those mentioned above can be used. As the unsaturated polyester, those having a number average molecular weight of preferably 500 to 6000, more preferably 1000 to 4000 can be used.

Further, a resin obtained by modifying the above unsaturated polyester with an epoxy compound such as glycidyl methacrylate, bisphenol A type epoxy, or an isocyanate compound such as toluene diisocyanate or isopropenyl-dimethyl-benzyl isocyanate may be used.

Further, the above α, β-unsaturated dicarboxylic acid,
It is also preferable to use a dicyclopentadiene-modified unsaturated polyester obtained by adding dicyclopentadiene to a saturated dicarboxylic acid and a polyhydric alcohol and reacting them together. The method of synthesizing the dicyclopentadiene-modified resin is not particularly limited, but it is desirable to use a polyester obtained by a method of adding dicyclopentadiene to a carboxy group derived from maleic acid because of high reactivity.

Further, a glycol decomposition product obtained by reacting recovered polyethylene terephthalate (PET) with a polyhydric alcohol at a high temperature is used as a main raw material, and the above α, β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol, particularly hydrogen. If the present invention is applied to the PET unsaturated polyester obtained by reacting with the modified bisphenol A, it can be used without any problem.

The vinyl ester resin which can be used in the present invention is a reaction product obtained by reacting an epoxy resin with an unsaturated monobasic acid. Examples of the epoxy resin include glycidyl ethers of polyhydric phenols such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated epoxy resin, and dipropylene glycol diglycidyl. Ether, diglycidyl ether of alkylene oxide adduct of bisphenol A, glycidyl ether of polyhydric alcohol such as hydrogenated bisphenol A diglycidyl ether, diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate Ester, diglycidyl p-oxybenzoic acid, glycidyl ester such as dimer glycidyl ester, tetraglycidyl diaminodiphenyl meta , Tetraglycidyl m- xylylenediamine, triglycidyl P- aminophenol, N, glycidyl amines such as N- diglycidyl aniline, and heterocyclic epoxy resins such as triglycidyl isocyanurate. These epoxy resins may be used alone or in combination of two or more kinds.

Examples of unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethylmalate, monomethylfumarate,
Examples thereof include monocyclohexyl fumarate and sorbic acid. These acids may be used alone or in combination of two or more.

Further, the obtained vinyl ester resin is treated with an acid anhydride such as maleic anhydride, succinic anhydride or acetic anhydride, toluene diisocyanate or isopropenyl-dimethyl-.
It may be modified with an isocyanate compound such as benzyl isocyanate.

The vinyl urethane resin usable in the present invention is an oligomer obtained from a polyol compound, an organic polyisocyanate compound and a hydroxyl group-containing (meth) acrylate. The polyol compound is a general term for compounds having a plurality of hydroxyl groups in the molecule, but a functional group having active hydrogen capable of reacting with an isocyanate group instead of a hydroxyl group, for example, a carboxyl group, an amino group, or a compound having a mercapto group. I do not care. Examples of the polyol compound include polyester polyol, polyether polyol, acrylic polyol, polycarbonate polyol, polyolefin polyol, castor oil polyol, caprolactone-based polyol, and the like,
Each may be used alone or in combination of two or more. The following compounds can be used as the organic polyisocyanate compound.

Specific examples of the organic polyisocyanate compounds include, but are not limited to, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate and naphthalene diisocyanate. , 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and the like are used. In addition, multimers obtained by converting various isocyanate compounds into isocyanurate are also included. These may be used alone or in combination of two or more.

The acrylic resin includes a thermoplastic acrylic polymer derived from a (meth) acrylic acid ester and a polymerizable unsaturated monomer containing (meth) acrylic acid ester as a main component and a polymerizable unsaturated monomer. It is composed. (Meth) acrylic acid ester as an essential component,
If necessary, another polymerizable unsaturated monomer copolymerizable with the above-mentioned (meth) acrylic acid esters is used in combination, and the monomer solution is obtained by polymerization. Since this acrylic polymer is used in the form of syrup dissolved in the polymerizable monomer, it preferably has a molecular weight of 100,000 or less, and can be obtained by a general polymerization method such as suspension polymerization or solution polymerization. .
Further, a syrup obtained by prepolymerizing 10 to 40% by weight of the monomer may be used as it is.

As typical examples of the polymerizable unsaturated monomer which can be used in combination with the radical copolymerizable unsaturated resin, styrenes, acrylic esters, methacrylic esters, diallyl phthalate esters, Known substances such as carboxylic acid vinyl esters and vinyl ethers can be used. However, the present invention is not limited to this, and various unsaturated monomers can be appropriately selected and used according to the application of the resin liquid and the required performance.

The blending amount of the polymerizable unsaturated monomer with respect to the radical copolymerizable unsaturated resin such as unsaturated polyester, vinyl ester resin, vinyl urethane resin or acrylic resin is not particularly limited, but is 10 to 10. 7
It is preferably within the range of 0% by weight, more preferably within the range of 20 to 50% by weight. The weight% ratio of radical copolymerizable unsaturated resin: polymerizable unsaturated monomer is preferably 30 to 90.
% By weight: 10 to 70% by weight, more preferably 50 to 80
% By weight: 20 to 50% by weight.

In the present invention, the addition polymerization type polymer (thermoplastic resin) mixed with the radical copolymerizable unsaturated resin
The material is not particularly limited, but a material that exhibits the desired effects of lowering shrinkage and improving physical properties (such as fracture toughness) can be appropriately selected and used according to the molding application, conditions and the like. If only representative examples are given, polystyrene-based resins containing styrene as a main component, for example, polystyrene, copolymers of styrene and (meth) acrylic acid ester, styrene-conjugated diene block copolymers, styrene- Examples include hydrogenated conjugated diene block copolymers.
In addition, styrene-free (meth) acrylic acid ester-based polymers, for example, polymethyl methacrylate, polyacrylic acid n-butyl ester and the like can be mentioned. Moreover, what made the double bond in these polymers react with other compounds can also be used.

The above-mentioned styrene-conjugated diene type block copolymer is a block copolymer composed of a styrene component and a conjugated diene component obtained by polymerizing styrene and a conjugated diene, and butadiene, isoprene, and 1,3-pentadiene or the like is used. Further, it may be a styrene-hydrogenated conjugated diene block copolymer obtained by hydrogenating these styrene-conjugated diene block copolymers. The constitutional unit of the block copolymer is not particularly limited, and includes a repeating unit of styrene and a conjugated diene such as styrene-conjugated diene, styrene-conjugated diene-styrene and conjugated diene-styrene-conjugated diene. Specific examples thereof include a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a styrene-ethylene / butylene block copolymer, a styrene-ethylene / propylene block copolymer and the like.

The amount of the addition polymerization type polymer used in the present invention is not particularly limited as long as it can achieve its purpose, but the weight of the radical copolymerizable unsaturated resin and the addition polymerization type polymer is not limited. % Ratio is preferably 95/5 to 60 /
40, more preferably 85/15 to 70/30% by weight.

In the present invention, the resin composition can be used as a mixture of a radical copolymerizable unsaturated resin, a polymerizable unsaturated monomer, an addition polymer and a compatibilizer. Depending on the method of use, the addition polymerization type polymer may be added later to the resin composition comprising the radical copolymerizable unsaturated resin, the polymerizable unsaturated monomer and the compatibilizer.

If necessary, a polymerization inhibitor, a curing agent, a filler, a reinforcing material, an internal release agent, a coloring agent and various other additives can be added to the resin composition of the present invention.
For example, the polymerization inhibitor is not particularly limited, and a conventionally known polymerization inhibitor can be used. Specifically, hydroquinone, pt-butylcatechol,
t-butyl hydroquinone, toluhydroquinone, p-
Examples thereof include benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, and copper chloride. Only one kind of these polymerization inhibitors may be used, or two or more kinds thereof may be appropriately mixed and used. The amount of the polymerization inhibitor added is not particularly limited, but is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the resin composition.

The curing agent is not particularly limited, and conventionally known curing agents can be used. For example, one or more kinds selected from a heat curing agent, an ultraviolet curing agent, an electron beam curing agent and the like can be mentioned. The amount of the curing agent used is preferably 0.
It is 1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight.

Examples of the thermosetting agent include organic peroxides, specifically diacyl peroxide type, peroxy ester type, hydroperoxide type, ketone peroxide type, alkyl perester type and percarbonate type compounds. Known materials such as the above are used and are appropriately selected according to molding conditions. The amount used is preferably 0.1 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the resin composition.

The UV curing agent is a photosensitizing substance. Specifically, known compounds such as acylphosphine oxide-based compounds, benzoin ether-based compounds, benzophenone-based compounds, acetophenone-based compounds, and thioxanthone-based compounds are used, and are appropriately selected according to molding conditions. Examples of electron beam curing agents include halogenated alkylbenzenes and disulfide compounds. The amount used thereof is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the resin composition,
It is particularly preferably 0.5 to 3 parts by weight.

The additive (hardening accelerator) that is used in combination with the above-mentioned hardening agent to accelerate hardening is not particularly limited, but examples thereof include metal salts such as cobalt naphthenate and cobalt octenoate, and N. , N-dimethylaniline,
Examples include tertiary amines such as N, N-di (hydroxyethyl) paratoluidine and dimethylacetoacetamide,
It is selected and used as necessary. The amount used is preferably 0.01 to 2 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the resin composition.

As the fillers that can be used in the resin composition of the present invention, only typical ones will be exemplified. Calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, perlite, Examples thereof include baryta, silica, silica sand, dolomite, limestone, aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide, cold water stone, zirconium oxide, antimony trioxide, titanium oxide and molybdenum dioxide. These fillers are selected in consideration of workability, strength, appearance, economy of the obtained molded product, but calcium carbonate, aluminum hydroxide, silica, talc, etc. are often used. In addition, the surface-treated filler is also included in the filler. The amount used is preferably 50 to 300 parts by weight, and particularly preferably 100 to 200 parts by weight, based on 100 parts by weight of the resin composition.

The reinforcing material that can be used in the resin composition of the present invention may be one usually used as a fiber reinforcing material,
For example, there are glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber, aromatic polyamide fiber, nylon fiber, and carbon fiber. Examples of these forms include chopped strands, chopped strand mats, rovings, and woven fabrics.
These fiber reinforcements are selected in consideration of the viscosity of the composition and the strength of the resulting molded product. The amount used is preferably 10 to 150 parts by weight, particularly preferably 20 to 100 parts by weight, based on 100 parts by weight of the resin composition.

Examples of the internal release agent that can be used in the resin composition of the present invention include higher fatty acids such as stearic acid,
Examples thereof include higher fatty acid salts such as zinc stearate, alkyl phosphates, and modified silicone oil. However, the release agent is not limited to these, and various release agents can be appropriately selected and used according to molding conditions. The amount used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the resin composition.

Specific examples of the colorants that can be used in the resin composition of the present invention include inorganic pigments such as titanium white and carbon black, and organic pigments such as phthalocyanine blue and quinacridone red. Various coloring agents can be used depending on the type. Generally, a pigment is often added as a toner in which unsaturated polyester resin or the like is uniformly dispersed. The amount used is preferably 0. 0 with respect to 100 parts by weight of the resin composition.
It is 1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight.

Other various additives include viscosity modifiers such as viscosity reducing agents, defoaming agents, silane coupling agents, air blocking agents such as paraffin, and commercially available products can be used.

Further, sheet molding compound (hereinafter abbreviated as SMC), bulk molding
When producing molding materials such as compounds (hereinafter abbreviated as BMC), thickeners such as metal oxides and hydroxides such as magnesium oxide and calcium hydroxide, and crude M
There are polyfunctional isocyanate compounds such as DI. However, the present invention is not limited to this, and various thickeners can be appropriately selected and used according to the use of the molding material and the required performance. Generally, magnesium oxide is used because it is easy to control the viscosity increase. The amount used is preferably 0.1 to 5 parts by weight, particularly preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the molding material.

The resin composition containing the above-mentioned compatibilizer, addition-polymerization polymer, radical-copolymerizable unsaturated resin, polymerizable unsaturated monomer, etc. of the present invention is a molding material (SMC, BMC).
Molding, spray molding, hand lay-up molding, casting, pultrusion molding, coating material (paint, putty,
It can be used as a sealing material or a lining material.

The molding material of the present invention comprises the above resin composition, a polymerization inhibitor, a curing agent, a filler and a fiber reinforcing material, and if necessary various additives such as an internal release agent and a colorant. Those added are preferable.

Molded products obtained from the molding material of the present invention include bathtubs, kitchen counters, vanities, waterproof pans, household equipment such as septic tanks, artificial marble, panels, corrugated sheets,
Examples include drawing materials, polymer concrete, civil engineering materials such as blades for wind power generation, ships such as boats and ships, parts for vehicles such as lamp reflectors, buttons, and daily necessities such as bowling balls.

According to the present invention, by improving the compatibility of the radical copolymerizable unsaturated resin and the shrinkage-reducing agent, which cannot be easily achieved by the prior art, and further preventing the separation,
It enables stable one-liquefaction of the resin mixture. Further, it is possible to provide a practical compatibilizer capable of eliminating defects during molding due to separation. Therefore, the resin composition using the compatibilizing agent of the present invention does not separate the low-shrinking agent, and the molding material has excellent homogeneity, and thus has no scumming, uniform coloring property and surface smoothness. In addition, it is possible to obtain an extremely high-quality molded product having excellent surface gloss and the like.

[0068]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, “part” in the text means part by weight.

(Synthesis Example 1) (Preparation of Compatibilizer <Graft Copolymer (A)> of the Present Invention) A 1 L flask equipped with a thermometer, a nitrogen introducing tube, a stirrer, a condenser and a dropping funnel was charged with a solvent. As xylene 20
0 g was charged and the temperature was raised to 120 ° C. under a nitrogen stream. Next, in 192 g of styrene, the number average molecular weight of the polydimethylsiloxane chain as a silicon chain-based macromonomer was 5000
Monomethacrylic acid ester (SILAPONE FM
-0721, manufactured by Chisso Co., Ltd.) 18 g, the number average molecular weight of the polyether chain is 40 as the polyether macromonomer.
00 g of monomethoxy-polyethylene oxide-monomethacrylic acid ester of 140 g and AI as a polymerization initiator
A premix liquid in which 1.6 g of BN (azobisisobutyronitrile) was dissolved was prepared. Next, this mixed solution was dropped from a dropping funnel over about 3 hours to carry out addition polymerization. After the dropping, the reaction was further continued for 8 hours while maintaining 120 ° C to obtain the target graft copolymer (A). After the reaction, the resulting resin solution was cooled to 40 ° C., 33 g of xylene was added,
A compatibilizer composition containing 60% by weight of the active ingredient was obtained. This is designated as compatibilizer solution SES-1. Obtained polymer (A)
The number average molecular weight measured by GPC was 12000.

(Synthesis Example 2) (Same as above) In the same manner as in Synthesis Example 1, xylene 200 g and styrene 1 were added.
92 g, monomethacrylic acid ester having a number average molecular weight of 1000 as a polydimethylsiloxane chain as a silicon chain macromonomer (SILAPONE FM-0711,
(Manufactured by Chisso Co.) 18 g, 140 g of monomethoxy-polyethylene oxide-monomethacrylic acid ester having a polyether chain number average molecular weight of 4000 as a polyether-based macromonomer, and 1.6 g of AIBN as raw materials, and subjected to addition polymerization at 120 ° C. Graft copolymer (A) was obtained. Further, in the same manner as in Synthesis Example 1, 33 g of xylene was added to obtain a compatibilizing agent composition containing 60% by weight of the active ingredient. This is designated as compatibilizing agent solution SES-2. The number average molecular weight of the obtained polymer (A) measured by GPC is 11,000.
Met.

(Synthesis Example 3) (Same as above) In the same manner as in Synthesis Example 1, xylene 200 g and styrene 2 were added.
73 g, a monomethacrylic acid ester having a number average molecular weight of polydimethylsiloxane chains of 5000 as a silicon chain macromonomer (SILAPONE FM-0721,
(Manufactured by Chisso Corporation) 7 g, 70 g of a monomethoxy-polyethylene oxide-monomethacrylic acid ester having a polyether chain number average molecular weight of 4000 as a polyether-based macromonomer, and AIBN of 1.6 g are used as raw materials and subjected to addition polymerization at 120 ° C. Graft copolymer (A) was obtained. Further, in the same manner as in Synthesis Example 1, 33 g of xylene was added to obtain a compatibilizing agent composition containing 60% by weight of the active ingredient. This is designated as compatibilizing agent solution SES-3. G of the obtained polymer (A)
The number average molecular weight measured by PC was 10,000.

(Synthesis Example 4) (Same as above) In the same manner as in Synthesis Example 1, 200 g of xylene and 1 of styrene were used.
75 g, monomethacrylic acid ester having a number average molecular weight of polydimethylsiloxane chain of 1,000 as a silicon chain-based macromonomer (SILAPONE FM-0711,
(Manufactured by Chisso Corporation) 35 g, 140 g of monomethoxy-polyethylene oxide-monomethacrylic acid ester having a polyether chain number average molecular weight of 6000 as a polyether-based macromonomer, and AIBN 1.6 g as raw materials, and addition polymerization is carried out at 120 ° C. Graft copolymer (A) was obtained. Further, in the same manner as in Synthesis Example 1, 33 g of xylene was added to obtain a compatibilizing agent composition containing 60% by weight of the active ingredient. This is designated as compatibilizing agent solution SES-4. The number average molecular weight of the obtained polymer (A) measured by GPC was 13,000.
Met.

(Synthesis Example 5) (Synthesis of Comparative Compatibilizer) In the same manner as in Synthesis Example 1, 200 g of xylene and styrene 2 were added.
10 g, monomethoxy-polyethylene oxide-monomethacrylic acid ester 140 having a polyether chain number average molecular weight of 4000 as a polyether macromonomer 140
g and AIBN 1.6 g as raw materials were subjected to addition polymerization at 120 ° C. to obtain a comparative graft copolymer. Further, in the same manner as in Synthesis Example 1, 33 g of xylene was added to give a solid content of 60.
A comparative compatibilizer composition was obtained that did not contain wt% silicon-based polymer chains. This is designated as compatibilizing agent solution SE-1. The number average molecular weight of the obtained polymer measured by GPC was 11,000.

(Synthesis example 6) (Preparation of low-contracting agent-polystyrene solution) 650 g of styrene was charged in the same flask as in synthesis example 1 and heated to 50 ° C. Under stirring, weight average molecular weight of about 25
Ten thousand polystyrene (Dick Styrene CR-3500, manufactured by Dainippon Ink & Chemicals, Inc.) and 350 g of hydroquinone were added and dissolved to obtain a resin solution having a solid content of 35% by weight. This is designated as a low-contracting agent solution LP-1.

(Synthesis Example 7) (Preparation of unsaturated resin-unsaturated polyester resin) 2 L equipped with a nitrogen gas introducing tube, a reflux condenser and a stirrer
Propylene glycol 168 in a glass flask
g, neopentyl glycol 208 g, hydrogenated bisphenol A 480 g, and fumaric acid 696 g are charged, and heating is started under a nitrogen stream. At an internal temperature of 200 ° C, a dehydration condensation reaction was carried out by a conventional method, and when the acid value reached 26 KOHmg / g, the mixture was cooled to 180 ° C and hydroquinone 0.2 g was added.
Is added. Furthermore, it cooled to 160 degreeC and obtained the unsaturated polyester. Next, this unsaturated polyester was dissolved in 890 g of styrene to obtain an unsaturated polyester resin liquid having a solid content of 60% by weight. This is designated as radically polymerizable unsaturated resin liquid VP-1.

(Synthesis Example 8) (Preparation of unsaturated resin-unsaturated polyester resin) In a 2 L flask similar to Synthesis Example 7, 2-methyl-1,
3 Propanediol 504g, Maleic anhydride 588
and 264 g of dicyclopentadiene having a purity of 95% are charged, and heating is started under a nitrogen stream. Pay attention to fever,
Raise the temperature. At an internal temperature of 200 ° C, a dehydration condensation reaction was carried out by a conventional method, and when the acid value reached 30 KOHmg / g, 1
Cool to 80 ° C. and add 0.19 g of hydroquinone. Furthermore, it cooled to 150 degreeC and obtained the unsaturated polyester. Next, this unsaturated polyester is mixed with styrene 856.
g to obtain an unsaturated polyester resin liquid having a solid content of 60% by weight. This is a radical polymerizable unsaturated resin liquid VP
-2.

(Synthesis Example 9) (Preparation of unsaturated resin-vinyl ester resin) 826 g of hydrogenated bisphenol A type epoxy resin (epoxy equivalent 410) was placed in a 2 L four-necked flask equipped with nitrogen and air introduction tubes. Methacrylic acid (174 g) and hydroquinone (0.4 g) were charged, and the temperature was raised to 90 ° C. under a gas flow in which nitrogen and air were mixed in a ratio of 1: 1. 2- here
2.0 g of methylimidazole was added, the temperature was raised to 105 ° C., and the reaction was performed for 10 hours. Thus, a vinyl ester resin was obtained. Next, this vinyl ester resin was dissolved in 666 g of styrene and 0.15 g of toluhydroquinone,
A vinyl ester resin liquid having a solid content of 60% by weight was obtained. This is referred to as radically polymerizable unsaturated resin liquid VP-3.

Evaluation of [Preparation of resin composition and stability of its compatibilizing effect] (Example 1) The unsaturated resin liquid (VP-
1) 80 parts, low-contracting agent liquid (LP-
1) 20 parts and the compatibilizer solution obtained in Synthesis Example 1 (SES
-1) 200 parts of 2 parts (about 1.2 parts as an active ingredient)
The mixture was placed in a glass bottle and mixed with a stirrer at 2500 rpm for 5 minutes to obtain a resin mixed solution (resin composition).

The resin mixture thus obtained is allowed to stand at room temperature, and samples are taken 1 day and 30 days after preparation. After dropping this sample solution on a slide glass and covering it with a cover glass,
After applying a load of 20 gf / cm ² for 2 minutes, the dispersed state is confirmed by an optical microscope. At that time, an image was taken and the average diameter of the low-contraction agent droplets was calculated from the obtained image. The attached standard scale was used as the calculation standard. Based on these results, the compatibilizing performance was classified into 5 stages and evaluated. Further, in order to confirm the dispersion form in the curing process, after preparing and mixing a liquid containing 0.02 g of a curing agent Perbutyl Z (manufactured by NOF Corporation) to 2 g of the sample liquid, an image was similarly taken with an optical microscope. To do. At this time, use a hot stage to slide the slide glass from 30 ℃ to 140 ℃.
Up to 30 ° C over about 15 minutes after heating at a rate of 20 ° C / min for another 4 minutes at 140 ° C. The changes in the dispersed morphology during that time were tracked. An image after cooling at 30 ° C. was evaluated as an image after completion of curing. The equipment used is as follows. Optical microscope: Nikon, FX, 40x objective lens observation. Hot stage: Mettler, FP-82 Digital camera: Fuji Photo Film, HC-300 [Evaluation of compatibility] 1: Droplet average diameter is 10 μm or more. 2: The average diameter of the droplets is 5 μm or more and less than 10 μm. 3: The average diameter of the droplets is 3 μm or more and less than 5 μm. 4: The average diameter of the droplets is less than 3 μm. The compatibility of the composition obtained in Example 1 before curing was 4 after 1 day and 30 days after preparation. 1 day after preparation,
Good dispersion stability was also exhibited in the curing trace after 30 days, and the compatibility after the completion of curing was 4, confirming good compatibility.

(Examples 2 to 4) Resin compositions were prepared according to Example 1 except that the compatibilizing agent composition was changed to (SES2 to 4) obtained in Synthesis Examples 2 to 4. The compatibility of this liquid was evaluated in the same manner as in Example 1. The results, including those of Example 1, are shown in Table 1.

Comparative Example 1 A resin composition was prepared in the same manner as in Example 1 except that the compatibilizer composition was changed to (SE-1) obtained in Synthesis Example 5. The compatibility of this liquid was evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0082]

[Table 1]

<Explanation of Symbols in Table> SM: Styrene, P
EO: polyethylene oxide, DMSi: polydimethylsiloxane, PS: polystyrene, UP: unsaturated polyester resin

(Examples 5 and 6) A resin composition was prepared according to Example 1 except that the unsaturated resin solution was changed to (VP-2 to 3) obtained in Synthesis Examples 8 and 9. . The stability of this solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 2 and 3 A resin composition similar to Comparative Example 1 was prepared except that the unsaturated resin solution was changed to (VP-2 to 3) obtained in Synthesis Examples 8 and 9. The compatibility of this liquid was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0086]

[Table 2]

<Explanation of Symbols in Table> SM: Styrene, P
EO: polyethylene oxide, DMSi: polydimethylsiloxane, PS: polystyrene, UP: unsaturated polyester resin, VE: vinyl ester resin.

(Examples 7 and 8) The compatibilizer composition was obtained in Synthesis Example 3 (SES-3), and the unsaturated resin liquid was obtained in Synthesis Examples 8 and 9 (VP-2, 3). A resin composition was prepared in the same manner as in Example 1 except that The stability of this solution was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

[0089]

[Table 3]

<Explanation of Symbols in Table> SM: Styrene, P
EO: polyethylene oxide, DMSi: polydimethylsiloxane, PS: polystyrene, UP: unsaturated polyester resin, VE: vinyl ester resin.

Example 9 (Preparation of molding material and molded article) To 80 parts of the unsaturated resin (VP-1) obtained in Synthesis Example 7, the shrinkage reducing agent liquid (LP- 1) 20
Part, the compatibilizing agent solution (SES-1) 2 obtained in Synthesis Example 1
Parts, parabenzoquinone 0.06 parts, zinc stearate 4
Parts, calcium carbonate 140 parts, pigment toner (Politon Gray PT-8809, manufactured by Dainippon Ink and Chemicals) 10
Parts and a curing agent BIC-75 (manufactured by Kayaku Akzo Co., Ltd.) were mixed and sufficiently stirred to form a compound until uniformly dispersed. One day after the preparation of the obtained compound, 1.0 part of magnesium oxide was added as a thickening agent, mixed and stirred, and then impregnated into a glass fiber having a fiber length of 1 inch as a reinforcing material to obtain a sheet-like SMC (molding material). To get This SMC
Both sides are protected with a polyethylene film, and are further packaged and stored with an aluminum vapor deposition film that does not allow styrene to pass through. The glass content (GC%) of this SMC is 2
It was set to 8%.

The SMC (molding material) thus obtained is aged at 40 ° C. for 24 hours, then allowed to stand at room temperature and stored. Three days after SMC production, the mold was adjusted to 145 ° C for the upper mold and 135 ° C for the lower mold, and the pressure was 70 kgf /
30 by pressing and holding at cm2 (contact pressure) for 5 minutes
It was molded into a flat plate having a size of 30 cm and a thickness of 3 mm. The scumming, uniform coloring property, surface smoothness, and gloss of the obtained molded product were evaluated by the following methods. The results are shown in Table 4.

[Evaluation of Appearance of Molding] Evaluation of Scumming: The presence or absence of scumming was visually determined. Evaluation of uniform colorability: Along with visual evaluation, a color difference meter (color machine Σ80 manufactured by Nippon Denshoku Industries Co., Ltd.) is used to measure L values at 12 points or more at 1 cm intervals on an arbitrary straight line of the molded product. The average value of the L values is calculated, and the variation (standard deviation) of the L values is calculated using it as a standard, which is used as an index. Evaluation of surface smoothness: visual evaluation and surface strain measuring instrument SURFM
ATIC (Tokyo Boeki Co., Ltd.) is used to measure the secondary differential coefficient of surface irregularities. Surface gloss: Visual and gloss meter (Murakami Color Research Laboratory: G
M26D) and evaluated by 60 ° gloss.

[0094] (Evaluation criteria): Good ◎ ＞ ○ ＞ △ ＞ × Bad       Uniform colorability: ⊚ = No color unevenness is visually observed, and variation in L value                      (Standard deviation) is 0.5 or less.                   ○ = Almost no color unevenness can be visually confirmed, but if the L value is                       Rippling (standard deviation) is 0.7 or less.                   Δ = Color unevenness can be visually confirmed, L value variation (standard deviation)                        ) Is greater than 0.7 and less than 1.0.                   × = Variable color unevenness can be visually confirmed and variation in L value                       (Standard deviation) is 1.0 or more.

[0095]       Surface smoothness: A = secondary differential coefficient of 500 or less.                   ◯ = Second derivative is 700 or less.                   Δ = Second derivative is more than 700 and less than 1000.                   X = The secondary differential coefficient is 1000 or more.

[0096]       Surface gloss: ◎ = 60 ° Gloss is 90 or more.                   ◯ = 60 ° Gloss is 85 or more.                   Δ = 60 ° Gloss is 80 or more and less than 85.                   X = 60 ° Gloss is less than 80.

(Example 10) Synthesis Example 3 of compatibilizer composition
Example 9 except that it was changed to (SES-3) obtained in
SMC was prepared in the same manner as above to obtain a molded product. Furthermore, the same evaluation was performed. The results are shown in Table 4.

Example 11 SMC was prepared in the same manner as in Example 9 except that the unsaturated resin was changed to (VP-2) obtained in Synthesis Example 8 to obtain a molded product. Furthermore, the same evaluation was performed. The results are shown in Table 4.

Comparative Example 4 SMC was prepared in the same manner as in Example 9 except that the compatibilizing agent composition obtained in Synthesis Example 5 was changed to SE-1 to obtain a molded product. The same evaluation was performed, and the results are shown in Table 4.

[0100]

[Table 4]

<Explanation of Symbols in Table> SM: Styrene, P
EO: polyethylene oxide, DMSi: polydimethylsiloxane, PS: polystyrene, UP: unsaturated polyester resin.

As is clear from the results shown in Tables 1 to 3, the compatibilizer solution (SES-1) satisfying the conditions of the present invention.
In Examples 1 to 8 in which Nos. 4 to 4) were used, a high compatibilizing effect was obtained, the change in the dispersed state with time was extremely small, and a stable dispersed resin liquid was obtained. On the other hand, Comparative Examples 1 to 1 using the compatibilizing agent solution (SE-1) that does not satisfy the conditions of the present invention
In No. 3, a stable compatibilizing effect cannot be obtained, and there is a tendency for the dispersion morphology to easily change over time.

As is clear from the results of Examples 9 to 11 shown in Table 4, the compatibilizing agent of the present invention alleviated the molding defects associated with the separation of the low-shrinking agent and showed no scumming. It was possible to obtain a molded product in which uniform coloring properties, surface smoothness, and surface gloss were highly achieved. Comparative Example 4
Since the requirements for the present invention were not satisfied, molding defects tended to occur due to changes over time in the dispersion form of the low-shrinking agent, and the quality of the molded product was somewhat inferior.

[0104]

INDUSTRIAL APPLICABILITY The compatibilizing agent of the present invention improves the compatibility of the radical copolymerizable unsaturated resin and the low-shrinking agent, which could not be easily obtained by the prior art, and stabilizes the fine dispersion. ,
The one-liquefied state of the resin mixture is more excellent, and defects during molding due to separation over time can be eliminated. The resin composition using the present technology does not have a low-shrinking agent separated, and its molding material has excellent homogeneity, and thus has no scumming and has uniform coloring property, surface smoothness, surface gloss, etc. It is possible to provide a molded product that is highly achieved and has an extremely high quality.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 101: 00 C08L 101: 00 F term (reference) 4F071 AA22X AA31 AA43 AA43X AA49 AA50X AA53 AA67X AA77 AA81 BA09 BB03 BC01 4J011 PA65 PA69 PA78 PA88 PA89 PA99 PB40 PC02 4J027 AB02 AB03 AB05 AB06 AB07 AB10 AB15 AB16 AB17 AB18 AB19 AB23 AB24 AB25 AB26 AC01 AC02 AC03 AC04 AC06 AF01 AF05 AJ01 BA05 ACB4903

Claims (13)

[Claims] 1. A compatibilizer for compatibilizing a radical copolymerizable unsaturated resin and an addition polymerization type polymer, which contains a styrene-based monomer as a main component and has a chain (A1) obtained by a polymerization reaction, A graft copolymer (A) in which a silicon-based polymer chain (A2) containing polyorganosiloxane as an essential component and a polymer chain (A3) containing polyoxyalkylene ether, polyester and / or polycarbonate as a main component are bonded. A compatibilizing agent comprising. 2. The number average molecular weight of the polymer chains (A2) and (A3) of the graft copolymer (A) is from 1000 to 2
The compatibilizing agent according to claim 1, which is 0000. 3. The polymer chain (A2) and (A3) are bonded to the chain (A1) via a (meth) acryloyl group or a styryl group bonded to each polymer chain. 2. The compatibilizer according to item 2. 4. The content of oxyethylene units (units) in the polymer chain (A3) of the graft copolymer (A) is 20 to 100% by weight, according to any one of claims 1 to 3. Compatibilizer. 5. The chain (A) in the graft copolymer (A).
1), the weight% ratio (A1 / A2 / A3) of the polymer chains (A2) and (A3) is 90 / 0.1 / 9.9 to 20.
The compatibilizer according to any one of claims 1 to 4, which is / 20/60. 6. A chain (A1) of the graft copolymer (A).
Polymerization of a compound having a (meth) acryloyl group or styryl group bonded to one end of the polymer chains (A2) and (A3) as the component forming the The compatibilizer according to any one of claims 1 to 5, which comprises a sexual site. 7. The polymer chain (A2) of the graft copolymer (A) has a silicon-based polymer chain containing polyorganosiloxane as a main component, and the chain (A) is attached to one end of the molecule.
1) A structure having a binding site with 1).
The compatibilizer according to any one of 1. 8. The polymer chain (A3) of the graft copolymer (A) is mainly composed of a polyoxyalkylene ether, polyester and / or polycarbonate polymer chain, and the chain (A1) is bonded to one end of the molecule. The compatibilizer according to any one of claims 1 to 7, which has a structure having moieties. 9. The graft copolymer (A) comprises a chain (A
1) an unsaturated monomer having a styrene-based monomer as a main component, a macromonomer having a (meth) acryloyl group or a styryl group at one end of the polymer chain (A2), and a piece of the polymer chain (A3) It is obtained by addition-copolymerizing a macromonomer having a (meth) acryloyl group or a styryl group at the terminal.
The compatibilizer according to any one of 1. 10. A radical-copolymerizable unsaturated resin composition comprising the compatibilizing agent according to claim 1, a radical-copolymerizable unsaturated resin, and a polymerizable unsaturated monomer. . 11. The compatibilizer according to claim 1, an addition polymerization type polymer, a radical copolymerizable unsaturated resin,
A radical-copolymerizable unsaturated resin composition comprising a polymerizable unsaturated monomer. 12. A molding material comprising the radical copolymerizable unsaturated resin composition according to claim 11. 13. A molded product using the molding material according to claim 12.